Cement compositions comprising aromatic sulfonated polymers and methods of using the same

ABSTRACT

A method of servicing a wellbore that penetrates a subterranean formation includes displacing a cement composition comprising an aromatic sulfonated polymer into the wellbore and allowing the cement composition to set. In an embodiment, a transition time of the cement composition is less than or equal to about 60 minutes, alternatively less than or equal to about 50 minutes, less than or equal to about 40 minutes, less than or equal to about 30 minutes, less than or equal to about 20 minutes, or less than or equal to about 10 minutes. Thus, the transition time may be short enough to inhibit a substantial amount of gas migration into the cement composition before it sets. In yet another embodiment, the cement composition exhibits a viscosity that increases from a value of 35 Bc (Bearden units) to about 100 Bc in about 10 minutes or less when the cement composition sets.

FIELD OF THE INVENTION

The present invention generally relates to well cementing, and more particularly to cement compositions comprising aromatic sulfonated polymers for reducing a transition time of the compositions and methods of cementing a wellbore using such cement compositions.

BACKGROUND OF THE INVENTION

Zonal isolation refers to the isolation of a subterranean formation or zone, which serves as a source of a natural resource such as gas, oil, or water, from other subterranean formations. To achieve isolation of a subterranean formation, a well bore is typically drilled down to the subterranean formation while circulating a drilling fluid through the wellbore. After the drilling is terminated, a string of pipe, e.g., casing, is run in the wellbore. Next, primary cementing is typically performed whereby a cement slurry is placed in the annulus and permitted to set into a hard mass, thereby attaching the string of pipe to the walls of the wellbore and sealing the annulus. Subsequent secondary cementing operations such as squeeze cementing may also be performed.

One problem commonly encountered during the placement of a cement slurry in a wellbore is unwanted gas migration from the subterranean zone into and through the cement slurry. Gas migration is caused by the behavior of the cement slurry during a transition phase in which the cement slurry changes from a true hydraulic fluid to a highly viscous mass showing some solid characteristics. When first placed in the annulus, the cement slurry acts as a true liquid and thus transmits hydrostatic pressure. However, during the transition phase, certain events occur that cause the cement slurry to lose its ability to transmit hydrostatic pressure. One of those events is the loss of fluid from the slurry to the subterranean zone. Another event is the development of static gel strength, i.e., stiffness, in the slurry. As a result, the pressure exerted on the formation by the cement slurry falls below the pressure of the gas in the formation such that the gas begins to migrate into and through the cement slurry. When gas migration begins, the cement slurry typically has a gel strength of about 100 lb_(f)/100 ft². The gas migration causes flow channels to form in the cement slurry. Eventually the gel strength of the cement slurry increases to a value sufficient to resist the pressure exerted by the gas in the formation against the slurry. At this point, the cement slurry typically has a gel strength of about 500 lb_(f)/100 ft². The cement slurry then sets into a solid mass.

Unfortunately, the flow channels formed in the cement during such gas migration remain in the cement once it has set. Those flow channels can permit further migration of gas through the cement even long after the cement is set. Thus, the cement residing in the annulus may be ineffective at maintaining the isolation of the adjacent subterranean formation. To overcome this problem, attempts have been made to design a cement slurry having a shorter transition time, i.e., the period of time during which gas migration into the slurry can occur, which is typically the time ranging from when the gel strength of the slurry is about 100 lb_(f)/100 ft² (pound force per hundred square foot) to when it is about 500 lb_(f)/100 ft². While cement slurries having shorter transition times have been developed, those slurries are typically very expensive to prepare. Further, their transition times are still longer than desired.

As such, there continues to be a need for improved methods of eliminating gas migration during well cementing to reduce the risk of compromising zonal isolation. It is therefore desirable to develop relatively inexpensive cement compositions having even shorter transition times.

SUMMARY OF THE INVENTION

A method of servicing a wellbore that penetrates a subterranean formation includes displacing a cement composition comprising an aromatic sulfonated polymer into the wellbore and allowing the cement composition to set. In embodiments, a transition time of the cement composition is less than or equal to about 60 minutes, less than or equal to about 50 minutes, less than or equal to about 40 minutes, less than or equal to about 30 minutes, less than or equal to about 20 minutes, or less than or equal to about 10 min. As such, the transition time may be short enough to inhibit a substantial amount of gas migration into the cement composition before it sets.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of thickening time for a cement composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Cement compositions or slurries may include at least one water soluble aromatic sulfonated polymer for reducing the transition times of the compositions. As used herein, the transition time of a cement composition is defined as the period of time after the composition is placed into a wellbore annulus during which the pressure exerted on the subterranean formation by the cement composition is less than the pressure of the gas in the formation such that gas migration into the composition can occur. The transition time is typically the time ranging from when the gel strength of the composition is about 100 lb_(f)/100 ft to when it is about 500 lb_(f)/100 ft². Due to the presence of the aromatic sulfonated polymer in the cement compositions, the transition times of the compositions are typically less than or equal to about 60 minutes, alternatively less than or equal to about 50 minutes, alternatively less than or equal to about 40 minutes, alternatively less than or equal to about 30 minutes, alternatively less than or equal to about 20 minutes, or alternatively less than or equal to about 10 minutes. As a result, a cement composition may be pumped to its desired location in a wellbore, e.g., the annulus, and allowed to set without being concerned that gas migration could compromise its ability to seal an area of the wellbore. That is, there is insufficient time for the gas to migrate into and through the cement composition and form flow channels therein. The water soluble aromatic sulfonated polymer thus serves as a gas migration control additive in the cement compositions.

As illustrated in the examples below, the cement compositions also exhibit a relatively constant viscosity for a period of time after they are initially prepared and while they are being placed in their intended locations in the wellbore. Eventually, the cement compositions quickly set such that the viscosity increases to equal to higher than above 70 Bearden units of Consistency (Bc) from about 35 Bearden units (Bc) in less than about 60 minutes. In an embodiment, the viscosity increases to its maximum in less than about 10 minutes. This sudden jump in viscosity is very desirable in preventing the gas migration because it indicates the quick formation of impermeable mass from a gelled state after placement. This behavior is often referred to as “Right Angle Set” and such cement compositions are called “Right Angle Set Cement Compositions.” In contrast, the viscosity of conventional cement compositions typically increases gradually over time to its maximum value.

Any suitable water soluble aromatic sulfonated polymer known in the art operable to provide the desired properties described herein may be employed in the cement compositions. In one embodiment, an aromatic sulfonated polymer comprises a polymeric backbone having sulfonated (i.e., salts of sulfonic acid functional groups) aromatic rings as pendant groups. Examples of such aromatic rings include phenyl rings, naphthyl, anthracenyl or phenanthrenyl rings. Examples of suitable aromatic sulfonated polymers include but are not limited to compounds having one of chemical Structures A-F where M is H, alkali or alkaline earth metal, or ammonium; partially or completely sulfonated polystyrenes such as those having Structure B; poly(styrene sulfonic acid) such as those having Structure A and its alkali or alkaline earth metal or ammonium salts where M=H, alkali or alkaline earth metal, or ammonium; polymers obtained by polymerizing monomers comprising allyloxybenzenesulfonic acid (structure not shown); copolymers of styrene and sulfonated styrene such as those having Structure B; sulfonated gilsonites; sulfonated lignin; copolymers comprising sulfonated styrene, sulfonated alpha-methylstyrene, sulfonated vinyl toluene and the like; and combinations thereof. In some embodiments such aromatic sulfonated polymers may contain small amounts other comonomers such as maleic anhydride, acrylic acid, AMPS (2-acrylamido-2-methyl-1-propane sulfonic acid), methallysulfonic acid, or combinations thereof. Such additional monomers may be present in less than 10 molar percent of the monomer content of the aromatic sulfonated polymer. Of these poly(styrene sulfonic acid) and its alkali metal salts are preferred. Suitable commercially available water soluble aromatic sulfonated polymers include VERSA-TL 130, VERSA-TL-501, VERSA-TL 130, VERSA-TL 77, VERSA-TL 70, VERSA-TL 501 from ALCO Chemical, a division of National Starch and Chemical Company, Chattanooga, Tenn., SOLTEX SHALE INBIBITOR from Drilling Specialties Company, The Woodlands, Tex., and BOREMASTER from Setac Chemical Corporation, Lafayette, La. In an embodiment, water soluble aromatic sulfonated compounds may contain the sulfonated aromatic ring as part of the polymer back bone. Such aromatic sulfonated polymers may comprise a linear polymer containing three kinds of unit bonds, i.e., an arylene bond, an ether bond, and a sulfone bond. Examples of such aromatic sulfonated polymers include those represented by the following Structures C-F. It is not necessary that all the aromatic rings are sulfonated in the polymers containing the aromatic rings as part of the polymer back bone. The degree of sulfonation is such that the whole polymer becomes water soluble either in the acid form or when converted to an alkali or alkaline earth metal or ammonium salt. For the purpose of the present invention, a sulfonated polymer with solubility of greater than 1% in cement composition at ambient temperature is considered water soluble.

The aromatic sulfonated polymers of the present invention are compatible with other components commonly used in cement compositions. The amount of aromatic sulfonated polymer present in the cement composition may be in a range of from about 0.1% to about 5%, from about 1.1% to about 2%, or from about 1.2% to about 1.5%, all percentages being by weight of the cement (bwoc).

The cement compositions may further include cement such as hydraulic cement, which includes calcium, aluminum, silicon, oxygen, and/or sulfur and which sets and hardens by reaction with water. Examples of hydraulic cements include but are not limited to a Portland cement, a pozzolan cement, a gypsum cement, a high alumina content cement, a silica cement, a high alkalinity cement, and combinations thereof. The cement may be, for example, a API Class A, C, G, or H Portland cement. In an embodiment, ultrafine particle cement (mean particle size equal to less than 5 microns) may be used. A sufficient amount of water may also be added to the cement to form a pumpable cementitious slurry. The water may be fresh water or salt water, e.g., an unsaturated aqueous salt solution or a saturated aqueous salt solution such as brine or seawater. The water may be present in the amount of 30% to 150% by weight of cement preferably in 40% to 110% by weight of cement.

In an embodiment, the cement the cement compositions may also include a high temperature strength retainment additive such as silica flour, which is commercially available from Halliburton Energy Services, Inc. under the tradename of SSA-1. Other high temperature strength retaining materials include silica materials, SILICALITE, SSA-2, and MICROSAND available from Halliburton Energy Services, Inc. Such materials may be used in amounts ranging from 5% to 45% by weight of cement.

In another embodiment, the cement compositions may additionally include a set retarder to increase the time required for the cement composition to set and thus provide a sufficient amount of time for the composition to be properly placed in the wellbore. Examples of suitable set retarders include, but are not limited to, lignosulfonate such as HR-5, a synthetic copolymer such as SCR-100, SCR-500, an organic acid retarder such as HR-25, carboxymethyhydroxyethyl cellulose, DIACEL LWL all commercially available from Halliburton Energy Services, Inc., and combinations thereof. Such retarders or suitable combinations of retarders may be used in amounts of 0.1% to about 3% by weight of cement depending on the temperature of application. In an embodiment, an amount of such retarders is added that is effective to retain fluidity and pumpability of cement slurries for 2-6 hrs under down hole conditions.

As deemed appropriate by one skilled in the art, additional additives may be added to the cement compositions for improving or changing the properties thereof. Examples of such additives include but are not limited to fluid loss control agents such as those sold under the brand HALAD by Halliburton Energy Services, Inc., defoamers, light weight additives such as glass or flyash spheres, fumed silica and Class F flyash, dispersing agents, weighting agents, foaming surfactants, and formation conditioning agents.

The foregoing cement compositions may be made by combining all of the components in any order and thoroughly mixing the components in a manner known to one skilled in the art. In an embodiment, the aromatic sulfonated polymer is available in an aqueous solution and is thus combined with the water before it is mixed with the cement to form a pumpable slurry. In an alternative embodiment, the aromatic sulfonated polymer is available as solid particles and is thus combined with the cement before water is introduced to the cement.

The foregoing cement compositions may be used in various cementing operations performed in a wellbore. In one embodiment, the cement compositions may be employed in primary cementing. Primary cementing first involves drilling a wellbore to a desired depth such that the wellbore penetrates a subterranean formation while circulating a drilling fluid through the wellbore. Subsequent to drilling the wellbore, at least one conduit such as a casing may be placed in the wellbore while leaving a space known as the annulus between the wall of the conduit and the wall of the wellbore. The drilling fluid may then be displaced down through the conduit and up through the annulus one or more times, for example, twice, to clean out the hole. A cement composition then may be conveyed downhole and up through the annulus, thereby displacing the drilling fluid from the wellbore. As discussed previously, the transition time of the cement composition is relatively short such that little or no gas migration into the composition can occur. The cement composition then quickly sets into an impermeable mass, forming a cement column that isolates an adjacent portion of the subterranean formation and provides support to the adjacent conduit.

In another embodiment, the cement compositions may be employed in a secondary cementing operation such as squeeze cementing, which is performed after the primary cementing operation. In squeeze cementing, a cement composition is forced under pressure into permeable zones through which fluid can undesirably migrate in the wellbore. Examples of such permeable zones include fissures, cracks, fractures, streaks, flow channels, voids, high permeability streaks, annular voids, or combinations thereof. The permeable zones may be present in the cement column residing in the annulus, a wall of the conduit in the wellbore, a microannulus between the cement column and the subterranean formation, and/or a microannulus between the cement column and the conduit. The transition time of the cement composition is relatively short such that the amount of gas migration into the composition is limited. The cement composition is allowed to set within the permeable zones, thereby forming an impermeable mass to plug those zones and prevent fluid from leaking therethrough.

EXAMPLES

The invention having been generally described, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages hereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims to follow in any manner. In the following examples, the cement compositions were prepared and tested in accordance with procedures described in the American Petroleum Institute (API) Specification 10A, 23^(rd) Edition, April 2002.

Example 1

Three cement compositions or slurries were prepared that contained different concentrations or types of aromatic sulfonated polymer, as shown below in Table 1. In particular, two of the cement compositions contained different concentrations of sulfonated polystyrene-A, and one contained sulfonated polystyrene-B. The sulfonated polystyrene-A and sulfonated polystyrene-B had different molecular weights as shown in Table 3. Sulfonated polystyrenes A, B and C were obtained ALCO Chemical, a Division of National Starch and Chemical Company. For each cement composition, the following components were blended with the aromatic sulfonated polymer: 100% class H cement, 48.3% water, 40% SSA-1 strength retainment additive, 45% HR-5 set retarder, and 0.25% HR-25 set retarder, all percentages being by weight of the cement. The liquid additives were added with mix water whereas solid additives were dry blended with cement.

As presented in Table 1 below, the rheology behavior of each slurry was tested at a temperature of 80° F. and atmospheric pressure using a FANN 35 viscometer.

Comparative Example 1

The same procedure followed in Example 1 was used to make and test a control cement composition containing a currently used gas migration control additive GASSTOP HT made from tannin grafted with acrylate monomers, which is commercially available from Halliburton Energy Services, Inc. Table 1 below also shows the results of the rheology test performed on this control cement composition.

TABLE 1 Additive GASSTOP Sulfonated Sulfonated Sulfonated HT Poly- Poly- Poly- (control) styrene-A styrene-A styrene-B Concentration,    1.1    1.1    0.55 1.1 % bwoc FANN 35 viscometer readings, centipoise @ 600 rpm  347+  347+  347+ 347+   @ 300 rpm  347+  347+ 242 300   @ 200 rpm 324 230 167 192   @ 100 rpm 202 144  89 96   @ 30 rpm 106  77  28 29   @ 6 rpm  24  17    5.6 6.5 @ 3 rpm  13  9    2.7 3.2 Based on the results in Table 1, the cement compositions containing the aromatic sulfonated polystyrene exhibited rheology behavior comparable to that of the GASSTOP HT gas migration control additive.

Example 2

Four cement compositions or slurries were prepared that contained different amounts or types of aromatic sulfonated polymer, as shown below in Table 2. In particular, two of the cement compositions contained different concentrations of sulfonated polystyrene-A, one contained sulfonated polystyrene-B, and one contained sulfonated gilsonite such as BORE MASTER from Setac Chemical Corporation, Lafayette, La.; or SOLTEX from Drilling Specialties Company, The Woodlands, Tex. For each cement composition, the following components were blended with the aromatic sulfonated polymer: 100% class H cement, 48.3% water, 40% SSA-1 strength retainment additive, 45% HR-5 set retarder, and 0.25% HR-25 set retarder, all percentages being by weight of the cement. Liquid additives were added with mix water whereas solid additives were dry blended with cement.

The thickening time required for each cement composition to achieve 70 Bearden units of consistency (Bc) was determined while continuously shearing the composition. While maintaining the cement composition in a static state, the time required for the viscosity to change from 35 Bc to 100 Bc was also determined. The thickening time indicates conversion of pumpable fluid state to a non-pumpable paste. The time lapse between 35 Bc to 100 Bc is also often considered as a measure of transition time indicating the viscosity change to form an impermeable solid mass from a gelled state. Moreover, the transition time required for the cement composition to change from having a static gel strength of 100 lb_(f)/100 ft² to having a static gel strength of 500 lb_(f)/100 ft² was determined at 300° F. and 10,000 psi using MINIMACS equipment supplied by Halliburton Energy Services, Inc. and described in more detail in Example 3.

The results of these thickening time and transition time tests are shown in Table 2 below. FIG. 1 is a plot of thickening time for the cement composition comprising 1.1\5 bwoc sulfonated polystyrene-A at 300° F. and 10,000 psi.

Comparative Example 2

The same procedure followed in Example 2 was used to make and test a control cement composition containing GASSTOP HT gas migration control additive. Table 2 below also shows the results of the rheology test performed on this control cement composition.

TABLE 2 Time to Concen- Thickening change from Transition time tration, time to 35 Bc to 100 lb_(f)/100 ft² to Additive % bwoc reach 70 Bc 100 Bc 500 lb_(f)/100 ft² GASSTOP HT 1.1 6 hrs. 9 min. 50-60 min. (control) Sulfonated 1.1 3 hrs. 2 min. 10 min. Polystyrene-A 40 min. Sulfonated 0.55 3 hrs. 2 min. Not Available Polystyrene-A 42 min. Sulfonated 1.1 4 hrs. 5 min. Not Available Polystyrene-B 55 min. Sulfonated 0.5 Not Not  8 min. Gilsonite Available Available

Based on the results depicted in Table 2, the sulfonated polystyrene-containing compositions and the sulfonated gilsonite-containing compositions exhibited much shorter times, required to change viscosity from 35 Bc to 100 Bc, and shorter transition times than the control cement composition containing a prior art material. Increasing the amount of sulfonated polystyrene-A used in the cement compositions did not affect the thickening time. As such, the polystyrene-A probably did not significantly affect the thickening time while the GLASSTOP HT additive probably retarded the thickening time. The sulfonated polystyrene and sulfonated gilsonite surprisingly had transitions times as low as 10 minutes and 8 minutes, respectively. Accordingly, such aromatic sulfonated polymers could serve as excellent gas migration control additives in cement compositions.

Example 3

Three cement compositions or slurries were prepared that contained different types of aromatic sulfonated polymers, as shown below in Table 3. In particular, the three cement compositions contained sulfonated polystyrene-A, sulfonated polystyrene-B, and sulfonated polystyrene-C, respectively. The molecular weights of these different sulfonated polystyrene materials are also shown in Table 3. For each cement composition, the following components were blended with 1.1% of the sulfonated polystyrene material: 100% class H cement, 35% SSA-1 strength retainment additive, 0.45% HR-5 set retarder, 0.25% HR-25 set retarder, and an effective amount of water to maintain a slurry density of 16.7 pounds per gallon, all percentages being by weight of the cement. The liquid additives were added with mix water whereas solid additives were dry blended with cement.

The transition time required for each cement composition to change from having a static gel strength of 100 lb_(f)/1100 ft² to having a static gel strength of 500 lb_(f)/100 ft² was determined. Further, the time required to reach 100 lb_(f)/100 ft² (referred to as Zero Gel Time) of each cement composition was determined according to the following procedure using a “MINIMACS” Instrument at 300° F. and 10,000 psi.

The static gel strength development test requires specialized equipment, such as the MACS Analyzer or the MINIMACS Analyzer. This equipment measures the shear resistance of a cement slurry under downhole temperature and pressure while the cement remains essentially static. The test is conducted by mixing the slurry and placing into the specialized testing device. The slurry is then stirred and heated to BHCT and downhole pressure according to the same schedule as the thickening time test. After the slurry reaches the BHCT, stirring is stopped and the slurry is allowed to essentially remain static. The stirring paddle is rotated at a rate of about 0.5°/min while the shear resistance on the paddle is measured. The shear resistance is correlated to the SGS (units are lb/100 ft²) and a plot of SGS development is made as a function of time.

Per the above test procedure, the “Zero Gel Time” is defined as the “time” the slurry takes to reach a static gel strength of 100 lb_(f)/100 ft² once the stirring is stopped and allowed to remain static. As illustrated in Table 3 below, the cement compositions containing the sulfonated polystyrene materials exhibited low transition times of less than or equal to 40 minutes.

TABLE 3 Molecular Zero Gel Transition Additive Weight Time (min.) Time (min.) Sulfonated 75,000 50 40 Polystyrene-A Sulfonated 200,000 60 30 Polystyrene-B Sulfonated 1,000,000 40 40 Polystyrene-C

While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Use of the term “optionally” with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim.

Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. The discussion of a reference herein is not an admission that it is prior art to the present invention, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein. 

1. A method of cementing a wellbore, comprising: (a) placing a cement composition comprising a water soluble aromatic sulfonated polymer into the wellbore, wherein the aromatic sulfonated polymer consists essentially of: (i) one or more monomers selected from the group consisting of partially or fully sulfonated polystyrene; polv(styrene sulfonic acid); a copolymer of styrene and sulfonated styrene; sulfonated gilsonite; sulfonated lignin; a copolymer comprising sulfonated styrene, sulfonated alpha-methylstyrene, allyloxybenzenesulfonic acid or sulfonated vinyl toluene; one or more compounds having one of chemical Structures A-F:

 where M is H, alkali or alkaline earth metal, or ammonium; and combinations thereof; and (ii) from 0 to, less than about 10 molar percent of one or more monomers selected from the group consisting of maleic anhydride, acrylic acid, 2-acrylamnido-2-methyl-1-propane sulfonic acid, methally sulfonic acid or combinations thereof; and (b) allowing the cement composition to set, wherein the cement composition has a transition time of less than or equal to about 60 minutes.
 2. The method of claim 1, wherein the cement composition has a transition time of less than or equal to about 40 minutes.
 3. The method of claim 1, wherein the cement composition has a transition time of less than or equal to about 20 minutes.
 4. The method of claim 1, wherein the cement composition has a transition time of less than or equal to about 10 minutes.
 5. The method of claim 1, wherein the viscosity of the cement composition increases from about 35 Bc to about 100 Bc in about 10 minutes or less when the cement composition sets.
 6. The method of claim 1, wherein the aromatic sulfonated polymer consists essentially of alkali metal salts of poly(styrene sulfonic acid). 